Two beta-diketone mononuclear Dy(III) compounds, formulated as Dy(BTFA)(3)(H2O)(2) (1) and Dy(BTFA)(3)(bpy) (2) (BTFA = 3-benzoy1-1,1,1-trifluoroacetone, bpy = 2,2 '-bipyridine), were prepared. Compound 1 can be identified to transform to 2 in the attendance of bpy coligand, when the local geometry symmetry of eight -coordinated Dy(III) ion changes from a dodecahedron (D-2d) in 1 to a square antiprism (D-4d) in 2. Fine-tuning structure aroused by auxiliary ligand has dramatical impact on magnetic properties of compounds 1 and 2. Magnetic investigations demonstrate that both 1 and 2 display dynamic magnetic relaxation of single-molecule magnets (SMMs) behavior with different effective barriers (Delta E/k(B)) of 93.09 K for 1 under zero direct -current (DC) field as well as 296.50 K for 1 and 151.01 K for 2 under DC field, respectively. As noticed, compound 1 possesses higher effective barrier than 2, despite 1 exhibiting a lower geometrical symmetry of the Dy(III) ion. Ab initio studies reveal that the Kramers doublet ground state is predominantly axial with the gZ tensors of two compounds matching the Ising-limit factor of 20 anticipated for the pure M-J = +/- 15/2 state. Electrostatic analysis confirms the uniaxial anisotropy directions, highlighting that the proper electrostatic distribution of the coordination sphere around Ln(III) center is the critical factor to improve the magnetic anisotropy and determine the dynamic behaviors of SMMs.